WO2018116889A1 - Composition de résine cristalline liquide pour relais montés en surface et relais monté en surface l'utilisant - Google Patents

Composition de résine cristalline liquide pour relais montés en surface et relais monté en surface l'utilisant Download PDF

Info

Publication number
WO2018116889A1
WO2018116889A1 PCT/JP2017/044425 JP2017044425W WO2018116889A1 WO 2018116889 A1 WO2018116889 A1 WO 2018116889A1 JP 2017044425 W JP2017044425 W JP 2017044425W WO 2018116889 A1 WO2018116889 A1 WO 2018116889A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystalline
resin composition
structural unit
crystalline resin
mol
Prior art date
Application number
PCT/JP2017/044425
Other languages
English (en)
Japanese (ja)
Inventor
博樹 深津
智弘 瀧
Original Assignee
ポリプラスチックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to JP2018520209A priority Critical patent/JP6416443B1/ja
Priority to CN201780064270.0A priority patent/CN109844027B/zh
Publication of WO2018116889A1 publication Critical patent/WO2018116889A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H45/00—Details of relays
    • H01H45/02—Bases; Casings; Covers

Definitions

  • the present invention relates to a liquid crystalline resin composition for surface-mounting relays and a surface-mounting relay using the same.
  • an insertion mounting type (through-hole type) relay is known as a relay used by being mounted on a printed circuit board.
  • the insertion mounting relay includes a terminal protruding vertically from the relay body, and is first placed on one surface of the printed board by inserting the terminal into a hole of the printed board. Thereafter, by soldering the terminals on the other surface of the printed board, the insertion mounting relay is fixed to the printed board so as to be electrically conductive.
  • a surface mount type relay has been developed as a new relay to be used by mounting on a printed circuit board (for example, Patent Document 1).
  • the terminal protruding vertically from the relay body is bent at a right angle so that the soldering surface is parallel to the relay body.
  • surface mount relays can be electrically connected by placing the above terminals on the solder pads provided on the conductor pattern on the surface of the printed circuit board and performing solder reflow processing without providing holes in the printed circuit board. Fixed to the printed circuit board.
  • the surface mount relay is fixed to the printed circuit board by the solder reflow process
  • the molded product constituting the surface mount relay for example, the base, the case, the bobbin, etc. is excellent so that it can withstand the solder reflow process. Heat resistance is required. Further, the surface mount relay is also required to maintain airtightness even after the solder reflow process.
  • the molded product, in particular, the base and the case are required to be bonded with high adhesive strength by an adhesive.
  • liquid crystalline polymer compositions are attracting attention in terms of excellent heat resistance, dimensional accuracy, fluidity, and the like.
  • the liquid crystal polymer composition may have a problem of blistering. That is, liquid crystalline polyesteramide, which is a liquid crystalline polymer, is often used as a material that requires heat treatment at a high temperature because it has good high-temperature thermal stability.
  • liquid crystalline polyesteramide which is a liquid crystalline polymer
  • the molded product is left in high temperature air and liquid for a long time, there arises a problem that fine blisters called blisters are generated on the surface. This phenomenon is caused by the fact that the decomposition gas generated when the liquid crystalline polyesteramide is in a molten state is brought into the molded product, and then the gas expands when the high-temperature heat treatment is performed.
  • the generation of blisters can be reduced by sufficiently degassing the vent hole during melt extrusion of the material, or by not allowing the material to stay in the molding machine for a long time during molding.
  • the range of conditions is very narrow, and it is not sufficient to obtain a molded product in which generation of blisters is suppressed, that is, a molded product having blister resistance.
  • the fundamental solution to blister generation requires improvement of the quality of the liquid crystalline polyester amide itself, and the known liquid crystalline polyester amide and methods using it are insufficient to solve the problem of blister generation.
  • the liquid crystalline polymer composition may have a problem that the filler protrudes from the surface of the molded article of the composition and further desorbs, thereby causing a functional disorder such as poor conduction of the product.
  • the present invention has been made in view of such circumstances, and is surface mounted that provides a molded product that has excellent heat resistance, suppresses the generation of blisters and fillers, and can be bonded with high adhesive strength by an adhesive. It is an object of the present invention to provide a liquid crystalline resin composition for relay, a surface mount relay component comprising the composition, and a surface mount relay including the component.
  • the inventors of the present invention combined a liquid crystalline polymer containing a predetermined amount of a specific structural unit and a fibrous filler so that the weight average fiber length of the fibrous filler is 50 to 170 ⁇ m. It has been found that the above problem can be solved by setting the content of a fraction having a length of 20 to 200 ⁇ m to 70% by mass or more. Specifically, the present invention provides the following.
  • a liquid crystalline resin composition for a surface mount relay comprising (A) a liquid crystalline polymer and (B) a fibrous filler,
  • the (A) liquid crystalline polymer comprises the following structural units (I) to (V) as essential structural components,
  • the content of the structural unit (I) is 50 to 69 mol% with respect to all the structural units,
  • the content of the structural unit (II) is 9.2 to 22.5 mol% with respect to all the structural units,
  • the content of the structural unit (III) is 2.5 to 6.3 mol% with respect to all the structural units,
  • the content of the structural unit (IV) is 8.5 to 24 mol% with respect to all the structural units,
  • the content of the structural unit (V) is 1 to 7 mol% with respect to all the structural units,
  • the total number of moles of the structural unit (II) and the structural unit (III) is 1 to 1.06 times the total number of moles of the structural unit (IV) and the structural unit (V), or the structural unit ( IV
  • a component for surface mount relay comprising the composition according to (1) or (2).
  • the liquid crystalline resin composition for surface-mounting relays which has excellent heat resistance, suppresses generation of blisters and detachment of filler, and gives a molded product that can be bonded with high adhesive strength by an adhesive, It is possible to provide a surface mount relay component made of the composition, and a surface mount relay including the component.
  • FIG. 1A is a perspective view schematically showing an embodiment of a surface mount relay according to the present invention
  • FIG. 1B is a partial cross-sectional view showing an AA cross section of FIG.
  • FIG. 2A and FIG. 2B are side views schematically showing a state where the embodiment of the surface mount relay according to the present invention is mounted on a printed board.
  • FIG. 3A is a diagram for explaining a method for producing a sample for evaluating the adhesive strength
  • FIG. 3B is a diagram for explaining a method for evaluating the adhesive strength.
  • the liquid crystalline resin composition for a surface-mount relay contains a predetermined amount of a specific liquid crystalline polymer and a fibrous filler, and the fibrous filler has a weight average fiber length of 50 to 170 ⁇ m.
  • the content of the fraction having a fiber length of 20 to 200 ⁇ m is 70% by mass or more
  • the surface mount relay includes a base and a terminal protruding from the base, and the terminal is attached to the printed circuit board.
  • This is a surface mount relay that is soldered.
  • the component which comprises the liquid crystalline resin composition which concerns on this invention is demonstrated.
  • the composite resin composition in the present invention includes a liquid crystalline polymer that is the above-mentioned wholly aromatic polyester amide. Since the wholly aromatic polyester amide has a low melting point, the processing temperature can be lowered and the generation of decomposition gas during melting is suppressed. As a result, in the molded product obtained by molding the composite resin composition containing the wholly aromatic polyester amide, blister generation is suppressed and blister resistance is improved.
  • a liquid crystalline polymer can be used individually by 1 type or in combination of 2 or more types.
  • the wholly aromatic polyester amide in the present invention comprises the following structural unit (I), the following structural unit (II), the following structural unit (III), the following structural unit (IV), and the following structural unit (V).
  • the structural unit (I) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as “HBA”).
  • HBA 4-hydroxybenzoic acid
  • the wholly aromatic polyester amide in the present invention contains 50 to 69 mol% of the structural unit (I) with respect to all the structural units.
  • the content of the structural unit (I) is less than 50 mol% or exceeds 69 mol%, at least one of heat resistance and manufacturability tends to be insufficient.
  • the structural unit (II) is derived from 1,4-phenylenedicarboxylic acid (hereinafter also referred to as “TA”).
  • TA 1,4-phenylenedicarboxylic acid
  • the wholly aromatic polyester amide in the present invention contains 9.2 to 22.5 mol% of the structural unit (II) with respect to all the structural units. When the content of the structural unit (II) is less than 9.2 mol% or exceeds 22.5 mol%, at least one of heat resistance and manufacturability tends to be insufficient.
  • the structural unit (III) is derived from 1,3-phenylenedicarboxylic acid (hereinafter also referred to as “IA”).
  • the wholly aromatic polyester amide in the present invention contains 2.5 to 6.3 mol% of the structural unit (III) with respect to all the structural units.
  • the content of the structural unit (III) is less than 2.5 mol% or exceeds 6.3 mol%, at least one of heat resistance and manufacturability tends to be insufficient.
  • the structural unit (IV) is derived from 4,4′-dihydroxybiphenyl (hereinafter also referred to as “BP”).
  • BP 4,4′-dihydroxybiphenyl
  • the wholly aromatic polyester amide in the present invention contains 8.5 to 24 mol% of the structural unit (IV) with respect to all the structural units. If the content of the structural unit (IV) is less than 8.5 mol% or exceeds 24 mol%, at least one of heat resistance and manufacturability tends to be insufficient.
  • the structural unit (V) is derived from N-acetyl-p-aminophenol (hereinafter also referred to as “APAP”).
  • the wholly aromatic polyester amide in the present invention contains 1 to 7 mol% of the structural unit (V) with respect to the total structural units.
  • the content of the structural unit (V) is less than 1 mol%, the heat resistance is good, but the manufacturability tends to be insufficient. If the content of the structural unit (V) exceeds 7 mol%, at least one of heat resistance and manufacturability tends to be insufficient.
  • the total number of moles of the structural unit (II) and the structural unit (III) is the structural unit (IV) and the structural unit. 1 to 1.06 times the total number of moles of unit (V) (hereinafter also referred to as “number of moles 2A”), or the total number of moles of structural unit (IV) and structural unit (V)
  • the number is 1 to 1.06 times the total number of moles of the structural unit (II) and the structural unit (III).
  • the number of moles 1A is preferably 1 to 1.025 times the number of moles 2A, or the number of moles 2A is preferably 1 to 1.025 times the number of moles 1A.
  • the wholly aromatic polyester amide in the present invention contains a specific amount of each of the specific structural units (I) to (V) with respect to all the structural units, and has a mole number of 1A and a mole. Since the ratio with the number 2A is in a specific range, the heat resistance and manufacturability are excellent in a good balance.
  • the wholly aromatic polyester amide of the present invention contains 100 mol% of the structural units (I) to (V) in total with respect to the total structural units.
  • DTUL a difference between a melting point and a deflection temperature under load
  • this difference is 110 ° C. or less, the heat resistance tends to increase, which is preferable.
  • DTUL is obtained by melt-kneading 60% by mass of the wholly aromatic polyester amide and 40% by mass of milled fiber having an average fiber diameter of 11 ⁇ m and an average fiber length of 75 ⁇ m at the melting point of the wholly aromatic polyester amide + 20 ° C. It is a value measured in the state of the liquid crystalline resin composition, and can be measured according to ISO75-1,2.
  • the difference is preferably more than 0 ° C. and 108 ° C. or less (eg, 65 ° C. or more and 108 ° C. or less), more preferably 71 ° C. or more and 107 ° C. or less.
  • the wholly aromatic polyester amide in the present invention is polymerized using a direct polymerization method, a transesterification method or the like.
  • a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, etc., or a combination of two or more of these are used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is used. Is preferably used.
  • an acylating agent for the polymerization monomer or a monomer having an activated terminal as an acid chloride derivative can be used.
  • the acylating agent include fatty acid anhydrides such as acetic anhydride.
  • various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, fatty acid metal salts, BF 3 Lewis acid salts such as are mentioned, and fatty acid metal salts are preferred.
  • the amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.003 to 0.2% by weight, based on the total weight of the monomers.
  • liquid paraffin high heat resistant synthetic oil, inert mineral oil, or the like is used as a solvent.
  • the reaction conditions are, for example, a reaction temperature of 200 to 380 ° C. and a final ultimate pressure of 0.1 to 760 Torr (that is, 13 to 101,080 Pa). Particularly in a melt reaction, for example, a reaction temperature of 260 to 380 ° C., preferably 300 to 360 ° C., a final ultimate pressure of 1 to 100 Torr (ie, 133 to 13,300 Pa), preferably 1 to 50 Torr (ie, 133 to 6,670 Pa). ).
  • all the raw material monomers HBA, TA, IA, BP, and APAP
  • the acylating agent can be charged into the same reaction vessel to start the reaction (one-stage system)
  • the APAP hydroxyl group can be acylated with an acylating agent and then reacted with the carboxyl groups of TA and IA (two-stage system).
  • the melt polymerization is performed after the inside of the reaction system has reached a predetermined temperature, and the pressure reduction is started to a predetermined degree of pressure reduction. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the total aromatic polyester amide is discharged from the reaction system through a normal pressure from a reduced pressure state to a predetermined pressure state.
  • the wholly aromatic polyester amide produced by the above polymerization method can further increase the molecular weight by solid-phase polymerization that is heated in an inert gas at normal pressure or reduced pressure.
  • Preferred conditions for the solid phase polymerization reaction are a reaction temperature of 230 to 350 ° C., preferably 260 to 330 ° C., and a final ultimate pressure of 10 to 760 Torr (ie 1,330 to 101,080 Pa).
  • the process for producing a wholly aromatic polyester amide according to the present invention comprises acylating 4-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol with a fatty acid anhydride in the presence of a fatty acid metal salt.
  • the amount of 4-hydroxybenzoic acid used is 50 to 69 mol%
  • the amount of 1,4-phenylenedicarboxylic acid used is 9.2 to 22.5 mol%
  • the amount of 1,3-phenylenedicarboxylic acid used is 2.5 to 6.3 mol%
  • the amount of 4,4′-dihydroxybiphenyl used is 8.5 to 24 mol%
  • the amount of N-acetyl-p-aminophenol used is 1-7 mol% It is preferable that The total number of moles of 1,4-phenylenedicarboxylic acid and 1,3-phenylic acid
  • number of moles 2B 1 to 1.06 times the total number of moles of phenol (hereinafter also referred to as “number of moles 2B”), or the sum of 4,4′-dihydroxybiphenyl and N-acetyl-p-aminophenol
  • the number of moles is preferably 1 to 1.06 times the total number of moles of 1,4-phenylene dicarboxylic acid and 1,3-phenylene dicarboxylic acid,
  • the amount of the fatty acid anhydride used is 1.02 to 1.04 times the total hydroxyl equivalent of 4-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. preferable.
  • the fatty acid metal salt is an acetic acid metal salt and the fatty acid anhydride is acetic anhydride.
  • the mole number 1B is 1 to 1.025 times the mole number 2B, or the mole number 2B is more preferably 1 to 1.025 times the mole number 1B.
  • the wholly aromatic polyester amide in the present invention exhibits optical anisotropy when melted.
  • An optical anisotropy when melted means that the wholly aromatic polyester amide in the present invention is a liquid crystalline polymer.
  • the fact that the wholly aromatic polyester amide is a liquid crystalline polymer is an essential element for the wholly aromatic polyester amide to have both heat stability and easy processability.
  • the wholly aromatic polyester amides composed of the structural units (I) to (V) may not form an anisotropic melt phase depending on the constituent components and the sequence distribution in the polymer. Is limited to wholly aromatic polyester amides exhibiting optical anisotropy when melted.
  • melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the melting anisotropy can be confirmed by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere.
  • the liquid crystalline polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.
  • a nematic liquid crystalline polymer causes a significant decrease in viscosity at a melting point or higher, generally exhibiting liquid crystallinity at a melting point or higher is an index of workability.
  • the melting point is preferably as high as possible from the viewpoint of heat resistance, but in consideration of thermal degradation during polymer melt processing, heating capability of the molding machine, etc., it is preferable that the melting point is more than 340 ° C. and not more than 370 ° C. Become. More preferably, it is 345 to 365 ° C.
  • the liquid crystalline resin composition according to the present invention contains the above liquid crystalline polymer in the liquid crystalline resin composition in an amount of 50 to 70% by mass with respect to the entire liquid crystalline resin composition.
  • the content of the liquid crystalline polymer is less than 50% by mass with respect to the entire liquid crystalline resin composition, the fluidity of the liquid crystalline resin composition is likely to deteriorate, and the surface mount relay obtained from the liquid crystalline resin composition This is not preferable because warpage deformation of a molded product such as an automotive part may increase.
  • the liquid crystalline resin composition according to the present invention preferably contains the liquid crystalline polymer in the liquid crystalline resin composition in an amount of 55 to 65% by mass, and 58 to 62% by mass with respect to the entire liquid crystalline resin composition. More preferably.
  • the liquid crystalline resin composition according to the present invention includes the above liquid crystalline polymer and a fibrous filler, and the fibrous filler has a weight average fiber length of 50 to 170 ⁇ m.
  • the fibrous filler Since the content of the fraction having a length of 20 to 200 ⁇ m is 70% by mass or more, the molded product obtained by molding the liquid crystalline resin composition has excellent heat resistance, generation of blisters and elimination of fillers. Is suppressed, and the adhesive can be bonded with high adhesive strength.
  • a fibrous filler can be used individually by 1 type or in combination of 2 or more types.
  • the fibrous filler in the present invention is not particularly limited, and is glass fiber, milled fiber, carbon fiber, asbestos fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, titanium. A potassium acid fiber etc. are mentioned. Milled fiber is preferred as the fibrous filler in the present invention because it is easy to suppress the detachment of the filler from the molded product while maintaining a high adhesive strength between the molded products obtained from the liquid crystalline resin composition.
  • the weight average fiber length of the fibrous filler is 50 to 170 ⁇ m, preferably 70 to 150 ⁇ m, more preferably 80 to 140 ⁇ m, and more preferably 100 to 140 ⁇ m. Even more preferably.
  • the weight average fiber length is less than 50 ⁇ m, the molded article obtained from the liquid crystalline resin composition is not sufficiently high in rigidity at high temperatures, and warpage deformation of the molded article may be increased.
  • the weight average fiber length is more than 170 ⁇ m, it is difficult to suppress the detachment of the filler from the molded product of the obtained liquid crystalline resin composition, which is not preferable.
  • the weight average fiber length of the fibrous filler means that the liquid crystalline resin composition is heated and ashed at 600 ° C. for 2 hours to obtain an ashing residue, and the ashing residue is converted to 5% by mass of polyethylene.
  • a dispersion liquid is obtained by dispersing in an aqueous glycol solution, and the weight average fiber length measured with an image measuring device is used for this dispersion liquid.
  • the fiber length 20 The content of the fraction having ⁇ 200 ⁇ m is 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more.
  • the upper limit of the said content rate is not specifically limited, It is 100 mass% or less, and 95 mass% or less may be sufficient.
  • the content is determined by heating the liquid crystalline resin composition at 600 ° C. for 2 hours to ash to obtain an ash residue, and dispersing the ash residue in a 5% by mass polyethylene glycol aqueous solution. A liquid is obtained, and this dispersion is measured from the fiber length distribution measured using an image measuring device.
  • the fiber diameter of the fibrous filler in the present invention is not particularly limited, and generally about 5 to 15 ⁇ m is used.
  • the liquid crystalline resin composition according to the present invention contains a fibrous filler in an amount of 30 to 50% by mass with respect to the entire liquid crystalline resin composition in the liquid crystalline resin composition.
  • the molded article such as a surface mount relay component obtained from the liquid crystalline resin composition has a low deflection temperature under load. This is not preferable because the high-temperature rigidity is not sufficient.
  • the content of the fibrous filler is more than 50% by mass with respect to the entire liquid crystalline resin composition, the fluidity of the liquid crystalline resin composition is deteriorated, and warpage deformation of the molded product may be increased. It is not preferable.
  • the fibrous filler in the present invention is preferably contained in the liquid crystalline resin composition in an amount of 35 to 45% by mass and more preferably in an amount of 38 to 42% by mass with respect to the entire liquid crystalline resin composition.
  • the liquid crystalline resin composition according to the present invention includes a plate-like filler, a nucleating agent, carbon black, a pigment such as an inorganic fired pigment, an antioxidant, a stabilizer, a plasticizer, a lubricant, a release agent. You may mix
  • the components in the liquid crystalline resin composition can be uniformly mixed, and the weight average fiber length of the fibrous filler is 50 to 170 ⁇ m.
  • the content is not particularly limited as long as the content of the fraction having a length of 20 to 200 ⁇ m can be 70% by mass or more, and can be appropriately selected from conventionally known methods for producing resin compositions.
  • each component is melt-kneaded and extruded using a melt-kneader such as a single-screw or twin-screw extruder, and then the obtained liquid crystalline resin composition is processed into a desired form such as powder, flakes, pellets, etc. The method of doing is mentioned.
  • liquid crystalline resin composition according to the present invention is excellent in fluidity, the minimum filling pressure at the time of molding is hardly excessive, and a surface mount relay component or the like can be preferably molded.
  • the melt viscosity of the liquid crystalline resin composition measured in accordance with ISO 11443 at a temperature 10 to 30 ° C. higher than the melting point of the liquid crystalline polymer at a shear rate of 1000 / second is more preferably 1 ⁇ 10 5 Pa ⁇ s or less (more preferably 5 Pa ⁇ s or more and 1 ⁇ 10 2 Pa ⁇ s or less) is preferable in terms of ensuring the fluidity of the liquid crystalline resin composition and preventing the filling pressure from becoming excessive at the time of molding of the surface mount relay component.
  • the surface mount relay component according to the present invention By molding the liquid crystalline resin composition according to the present invention, the surface mount relay component according to the present invention can be obtained.
  • the surface mount relay component according to the present invention is excellent in heat resistance, suppresses generation of blisters and detachment of filler, and can be bonded with high adhesive strength by an adhesive. Since the surface mount relay according to the present invention includes the above components, (1) it has excellent heat resistance and can withstand solder reflow processing, and (2) it can bond the base and the case with high adhesive strength, particularly with an adhesive. It is possible to maintain the properties even after the solder reflow treatment, and (3) the occurrence of blisters and the detachment of fillers are suppressed, and functional failures such as poor conduction are unlikely to occur.
  • FIG. 1A is a perspective view schematically showing an embodiment of a surface mount relay according to the present invention
  • FIG. 1B is a partial cross-sectional view showing an AA cross section of FIG.
  • the surface mount relay 1 includes a base 2, a case 3, a coil block 4, an armature block 5, and a terminal 6.
  • the base 2 includes a terminal 6 protruding from the base 2.
  • a case 3 is disposed on the outer peripheral portion of the upper surface of the base 2.
  • a coil block 4 and an armature block 5 are arranged in this order at the center of the upper surface of the base 2.
  • the case 3 is disposed so as to cover the outer peripheral portion of the upper surface of the base 2 and the coil block 4 and the armature block 5.
  • a coil block 4 and an armature block 5 are accommodated in a hollow container-like space formed by the base 2 and the case 3.
  • the coil block 4 includes a bobbin 41, a coil 42, and an iron core 43, and is arranged at the center of the upper surface of the base 2.
  • the bobbin 41 has a cylindrical portion penetrating in the long axis direction.
  • a coil 42 electrically connected to one end of a part of the terminal 6 is wound around the outer periphery of the bobbin 41, and the cylindrical portion of the bobbin 41 The iron core 43 is inserted into the.
  • the armature block 5 includes an armature connecting portion 51 and an armature 52 extending from the armature connecting portion 51 in opposite directions along the major axis direction of the bobbin 41 and disposed on the coil block 4.
  • the armature 52 is electrically connected to one end of another part of the terminal 6.
  • the terminal 6 has one end electrically connected to the coil 42 or the armature 52, and the other end connected to a printed circuit board 7 described later so as to be electrically conductive.
  • the terminal 6 protrudes from the base 2 and is soldered to the printed circuit board 7 as will be described later.
  • the base 2, the case 3, and the bobbin 41 are excellent in heat resistance, can be formed as a molded product that is prevented from generating blisters and detaching filler, and can be bonded with an adhesive with high adhesive strength.
  • the liquid crystalline resin composition according to the present invention is preferably used. That is, examples of the surface mount relay component according to the present invention include a base, a case, and a bobbin.
  • the coil block 4 and the armature block 5 are arranged in this order at the center of the upper surface of the base 2, and then the case 3 is arranged on the outer peripheral portion of the upper surface of the base 2. 3 can be manufactured by bonding them with an adhesive.
  • a method for mounting the surface mount relay 1 on the printed circuit board 7 will be described.
  • the terminal 6 protruding perpendicularly from the surface mount relay 1 is bent at a right angle so that the soldering surface is parallel to the surface mount relay 1. Therefore, the surface mount relay 1 places the terminal 6 on a solder pad (not shown) provided on the conductor pattern 8 on the surface of the printed circuit board 7 without providing a hole in the printed circuit board 7, and performs solder reflow processing. By performing, it is fixed to the printed circuit board 7 so as to be electrically conductive.
  • the tip of the terminal 6 protruding perpendicularly from the surface mount relay 1 is bent at right angles to the outside of the surface mount relay 1 has been shown.
  • the tip of the terminal 6 protruding perpendicularly from the surface mount relay 1 may be bent at a right angle toward the inside of the surface mount relay 1.
  • the liquid crystalline resin composition pellets were molded under the following molding conditions using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) to obtain test specimens (4 mm ⁇ 10 mm ⁇ 80 mm). .
  • Manufacturability The behavior when the polymer was discharged from the lower part of the polymerization vessel was observed, and the manufacturability was evaluated according to the following criteria. The results are shown in Tables 1 to 4. ⁇ : The polymer was discharged as a strand without any problem, and when this strand could be cut into a pellet, it was evaluated that the manufacturability was good. X: Manufacturability was evaluated to be poor when solidification or the like was caused in the container during polymerization and the polymer could not be discharged, or when the polymer could be discharged as a strand but the strand could not be cut.
  • the liquid crystalline polymer 1 is the liquid crystalline polymer obtained in Synthesis Example 1.
  • the liquid crystalline polymer 2 was manufactured as follows.
  • the melting point and melt viscosity of the pellet were measured under the following conditions.
  • Method for producing liquid crystalline polymer 2 A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a pressure reduction / outflow line was charged with the following raw material monomers, a metal catalyst, and an acylating agent, and nitrogen substitution was started.
  • the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further increased to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (ie, 667 Pa) over 20 minutes while distilling acetic acid, excess acetic anhydride, and other low-boiling components. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to change from a reduced pressure state to a normal pressure through a normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strand was pelletized to pelletize. The obtained pellet had a melting point of 355 ° C. and a melt viscosity of 10 Pa ⁇ s.
  • said manufacturer's nominal value differs from the value in Table 4 which is an actual measurement value in a composition.
  • extrusion conditions at the time of obtaining a liquid crystalline resin composition are as follows.
  • Extrusion conditions [Examples 1 and 2, Comparative Examples 1 and 3]
  • the temperature of the cylinder provided at the main feed port was 250 ° C., and the temperatures of the other cylinders were all 360 ° C. All liquid crystalline polymers were supplied from the main feed port.
  • the filler was supplied from the side feed port.
  • Comparative Example 2 The temperature of the cylinder provided at the main feed port was 250 ° C., and the temperatures of the other cylinders were all 380 ° C. All liquid crystalline polymers were supplied from the main feed port.
  • the filler was supplied from the side feed port.
  • the weight average fiber length of the fibrous filler in the liquid crystalline resin composition was measured by the following method. [Measurement of weight average fiber length] 5 g of liquid crystal resin composition pellets were heated at 600 ° C. for 2 hours to be incinerated. The ashing residue was sufficiently dispersed in a 5% by mass polyethylene glycol aqueous solution, then transferred to a petri dish with a dropper, and the fibrous filler was observed with a microscope. At the same time, the weight average fiber length of the fibrous filler was measured using an image measuring device (LUZEXFS manufactured by Nireco Corporation).
  • the content of the fraction having a fiber length of 20 to 200 ⁇ m was measured by the following method. [Measurement of content of fraction having fiber length of 20 to 200 ⁇ m] 5 g of liquid crystal resin composition pellets were heated at 600 ° C. for 2 hours to be incinerated. The ashing residue was sufficiently dispersed in a 5% by mass polyethylene glycol aqueous solution, transferred to a petri dish with a dropper, and the fiber length distribution of the fibrous filler was measured using an image measuring device (LUZEXFS manufactured by Nireco Corporation). In the fiber length distribution, the ratio of the fraction having a fiber length of 20 to 200 ⁇ m was read and used as the content.
  • the liquid crystalline resin composition was injection molded under the following molding conditions to obtain a molded product of 12.5 mm ⁇ 120 mm ⁇ 0.8 mm having a weld portion. A fragment obtained by dividing the molded product into two parts at the weld part was used as one specimen, and was sandwiched in a hot press at a predetermined temperature for 5 minutes. Thereafter, it was visually examined whether blisters were generated on the surface of the specimen.
  • the blister temperature was the maximum temperature at which the number of blisters generated was zero, and was evaluated according to the following criteria. ⁇ (Good): The blister temperature was 270 ° C. or higher. X (defect): The blister temperature was less than 270 ° C.
  • Molding machine Sumitomo Heavy Industries, SE100DU Cylinder temperature: 360 ° C. (Examples 1 and 2, Comparative Examples 1 and 3) 370 ° C. (Comparative Example 2) Mold temperature: 90 °C Injection speed: 33mm / sec
  • the liquid crystalline resin composition was injection molded under the following molding conditions to obtain a molded product of 12.5 mm ⁇ 120 mm ⁇ 0.8 mm having a weld portion.
  • the molded product obtained by dividing the molded product in two at the weld part was subjected to IR reflow under the following conditions, and then the detachment state of the fibrous filler was observed and evaluated according to the following criteria.
  • X (defect) The fibrous filler was detached. [Molding condition] Molding machine: Sumitomo Heavy Industries, SE100DU Cylinder temperature: 360 ° C.
  • the liquid crystalline resin composition was injection molded under the following molding conditions to obtain a test piece (ISO test piece Type 1A, thickness 4 mm). This test piece was divided into two parts and bonded together with an epoxy adhesive (Loctite 3128NH manufactured by Henkel) as shown in FIG. 3A (curing conditions: 80 ° C. ⁇ 30 minutes). Then, as shown in FIG.3 (b), the bonded test piece was installed, the load was applied in the arrow direction using the tensile tester, and adhesive strength was evaluated from the load when it peeled off. [Molding condition] Molding machine: Sumitomo Heavy Industries, SE100DU Cylinder temperature: 360 ° C.
  • the molded product molded from the liquid crystalline resin composition for surface mount relay according to the present invention is excellent in heat resistance, the generation of blister and the detachment of filler are suppressed, and the adhesive is highly bonded. We were able to bond with strength. Therefore, the liquid crystalline resin composition can be suitably used for the production of surface mount relay components and surface mount relays.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

L'invention concerne : une composition de résine cristalline liquide pour relais montés en surface, qui permet d'obtenir un article moulé ayant une excellente résistance à la chaleur, supprime les occurrences de cloques et de désorption de charge, et peut être collé à une force d'adhérence élevée par un adhésif ; un composant pour relais montés en surface l'utilisant ; et un relais monté en surface. Cette composition de résine cristalline liquide pour relais montés en surface comprend un polymère cristallin liquide (A) et une charge fibreuse (B). Le polymère cristallin liquide (A) est un amide polyester entièrement aromatique comprenant une quantité prescrite de motifs constitutifs (I)–(V) à titre de composants constitutifs essentiels et présentant une anisotropie optique pendant la fusion. La charge fibreuse (B) a une longueur de fibre moyenne en poids de 50 à 170 µm et contient au moins 70 % en poids d'une fraction ayant une longueur de fibre de 20 à 200 µm. Le relais monté en surface comprend une base et une borne faisant saillie à partir de la base, la borne étant soudée sur une carte de circuit imprimé.
PCT/JP2017/044425 2016-12-22 2017-12-11 Composition de résine cristalline liquide pour relais montés en surface et relais monté en surface l'utilisant WO2018116889A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2018520209A JP6416443B1 (ja) 2016-12-22 2017-12-11 表面実装リレー用液晶性樹脂組成物及びそれを用いた表面実装リレー
CN201780064270.0A CN109844027B (zh) 2016-12-22 2017-12-11 表面安装继电器用液晶性树脂组合物及使用其的表面安装继电器

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-250106 2016-12-22
JP2016250106 2016-12-22

Publications (1)

Publication Number Publication Date
WO2018116889A1 true WO2018116889A1 (fr) 2018-06-28

Family

ID=62627419

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/044425 WO2018116889A1 (fr) 2016-12-22 2017-12-11 Composition de résine cristalline liquide pour relais montés en surface et relais monté en surface l'utilisant

Country Status (4)

Country Link
JP (1) JP6416443B1 (fr)
CN (1) CN109844027B (fr)
TW (1) TWI716656B (fr)
WO (1) WO2018116889A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022168706A1 (fr) * 2021-02-05 2022-08-11

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102501091B1 (ko) * 2020-05-13 2023-02-17 포리프라스틱 가부시키가이샤 표면 실장 릴레이용 액정성 수지 조성물 및 이것을 이용한 표면 실장 릴레이

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6357634A (ja) * 1986-08-28 1988-03-12 バスフ　アクチェンゲゼルシャフト 全芳香族熱互変性ポリエステル
JPH06263857A (ja) * 1993-03-17 1994-09-20 Dainippon Ink & Chem Inc 共重合ポリエステル類およびその製造法
WO1998056578A1 (fr) * 1997-06-13 1998-12-17 Nippon Petrochemicals Company, Limited Composite lie et composition adhesive pour ledit composite
JP2005060455A (ja) * 2003-08-20 2005-03-10 Toray Ind Inc 液晶性ポリエステルアミドおよびその製造方法
JP2010138228A (ja) * 2008-12-09 2010-06-24 Nippon Oil Corp 液晶ポリエステル樹脂組成物
JP2013098313A (ja) * 2011-10-31 2013-05-20 Sumitomo Chemical Co Ltd 高電圧コイル
WO2013115168A1 (fr) * 2012-01-31 2013-08-08 Ｊｘ日鉱日石エネルギー株式会社 Amide de polyester à cristaux liquides, composition de résine d'amide de polyester à cristaux liquides, et article moulé
JP2016014137A (ja) * 2014-06-09 2016-01-28 住友化学株式会社 液晶ポリエステル樹脂組成物、コネクターおよび液晶ポリエステル樹脂組成物の製造方法
WO2017068869A1 (fr) * 2015-10-21 2017-04-27 ポリプラスチックス株式会社 Polyester amide entièrement aromatique, et son procédé de production
JP6133000B1 (ja) * 2015-10-21 2017-05-24 ポリプラスチックス株式会社 全芳香族ポリエステルアミド及びその製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5332188B2 (ja) * 2007-02-26 2013-11-06 住友化学株式会社 樹脂成形体及びその製造方法
JP5574896B2 (ja) * 2010-09-10 2014-08-20 ポリプラスチックス株式会社 原料組成又は製造条件決定方法
JP6357634B1 (ja) 2017-10-30 2018-07-18 株式会社クローバー・ネットワーク・コム 電話番号調査装置、同方法、同プログラム、同情報提供システム

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6357634A (ja) * 1986-08-28 1988-03-12 バスフ　アクチェンゲゼルシャフト 全芳香族熱互変性ポリエステル
JPH06263857A (ja) * 1993-03-17 1994-09-20 Dainippon Ink & Chem Inc 共重合ポリエステル類およびその製造法
WO1998056578A1 (fr) * 1997-06-13 1998-12-17 Nippon Petrochemicals Company, Limited Composite lie et composition adhesive pour ledit composite
JP2005060455A (ja) * 2003-08-20 2005-03-10 Toray Ind Inc 液晶性ポリエステルアミドおよびその製造方法
JP2010138228A (ja) * 2008-12-09 2010-06-24 Nippon Oil Corp 液晶ポリエステル樹脂組成物
JP2013098313A (ja) * 2011-10-31 2013-05-20 Sumitomo Chemical Co Ltd 高電圧コイル
WO2013115168A1 (fr) * 2012-01-31 2013-08-08 Ｊｘ日鉱日石エネルギー株式会社 Amide de polyester à cristaux liquides, composition de résine d'amide de polyester à cristaux liquides, et article moulé
JP2016014137A (ja) * 2014-06-09 2016-01-28 住友化学株式会社 液晶ポリエステル樹脂組成物、コネクターおよび液晶ポリエステル樹脂組成物の製造方法
WO2017068869A1 (fr) * 2015-10-21 2017-04-27 ポリプラスチックス株式会社 Polyester amide entièrement aromatique, et son procédé de production
JP6133000B1 (ja) * 2015-10-21 2017-05-24 ポリプラスチックス株式会社 全芳香族ポリエステルアミド及びその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022168706A1 (fr) * 2021-02-05 2022-08-11
JP7281023B2 (ja) 2021-02-05 2023-05-24 ポリプラスチックス株式会社 ファンインペラ用液晶性樹脂組成物及びそれを用いたファンインペラ

Also Published As

Publication number Publication date
CN109844027A (zh) 2019-06-04
JP6416443B1 (ja) 2018-10-31
TW201840715A (zh) 2018-11-16
CN109844027B (zh) 2020-08-04
JPWO2018116889A1 (ja) 2018-12-20
TWI716656B (zh) 2021-01-21

Similar Documents

Publication Publication Date Title
JP5165492B2 (ja) 平面状コネクター
JP6321899B1 (ja) 複合樹脂組成物、及び当該複合樹脂組成物から成形されたコネクター
JP6356938B1 (ja) 複合樹脂組成物、及び当該複合樹脂組成物から成形されたコネクター
JP5485216B2 (ja) 平面状コネクター
JP6157779B1 (ja) 全芳香族ポリエステルアミド及びその製造方法
JP6416442B1 (ja) 表面実装リレー用液晶性樹脂組成物及びそれを用いた表面実装リレー
JP6416443B1 (ja) 表面実装リレー用液晶性樹脂組成物及びそれを用いた表面実装リレー
JP6388749B1 (ja) 全芳香族ポリエステルアミド及びその製造方法
JP2018104507A (ja) 表面実装リレー用液晶性樹脂組成物及びそれを用いた表面実装リレー
JP6321898B1 (ja) 複合樹脂組成物、及び当該複合樹脂組成物から成形された電子部品
JP2018104506A (ja) 表面実装リレー用液晶性樹脂組成物及びそれを用いた表面実装リレー
JP6133000B1 (ja) 全芳香族ポリエステルアミド及びその製造方法
JP2018095684A (ja) 複合樹脂組成物、及び当該複合樹脂組成物から成形されたコネクター
JP2020041006A (ja) 全芳香族ポリエステル
WO2021229931A1 (fr) Composition de résine cristalline liquide pour des relais montés en surface, et relais monté en surface l'utilisant
JP6345373B1 (ja) 全芳香族ポリエステルアミド及びその製造方法
JP6189750B2 (ja) 全芳香族ポリエステル、ポリエステル樹脂組成物、及びポリエステル成形品

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018520209

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17884120

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17884120

Country of ref document: EP

Kind code of ref document: A1